Process for catalytic conversion of carbon oxides



Feb. 19, 1952 c. w. WATSON PROCESS FOR CATALYTIC CONVERSION OF CARBONOXIDES FledNOv. 25, 1945 Patented Feb. 19, 1952 PROCESS FOR CATALYTICCONVERSION OF "CARBON OXIDES Claude W. Watson, Scarsdale, N. Y.,assig'nor to The Texas Company, New York, N. Y., a corporation ofDelaware Application November 23, 1945, Serial No. 630,521

1 Claim. 1

This invention relates to the catalytic Vconversion of carbon monoxideand hydrogen into hy-` drocarbons, oxygenated hydrocarbons and the like.

The invention contemplates effecting the synthesis reaction in aplurality of reaction stages, each stage containing synthesis catalyst.Carbon monoxide Vand hydrogen are passed in contact With the catalyst ineach stage under conditions so as to effect substantial conversion intothe desired product. An eluent stream of reaction products containingcarbon dioxide and water is removed from each stage. Water is removedfrom each effluent stream and also Vsome hydrocarbons, if desired,following which each residual efuent stream, or fraction thereof,containing carbon dioxide in substantal amount is passed to itsrespective succeeding stage in the series. The eiiluent stream from theiinal stage is treated to remove carbon dioxide, Water and desiredproducts 'of reaction' 'and the removed "e: about 31 for a. reactiontemperature of about carbon dioxide is recycled advantageously to theinitial stage of the series.

More specifically, the invention contemplates effecting the synthesisreaction in a plurality of stages or zones. carbon monoxide, carbondioxide and hydrogen, and substantially free from Water, is separatelycharged to each stage orV zone in parallel ilow. Residual gases fromwhich water has been removed and which contain carbon dioxide, unreactedcarbon monoxide and hydrogen, as well as substantially Water-freeproducts of reaction, if desired, flow from a preceding stage toasucceeding stage in series now. Provision is made for removal of `Waterfrom the reactants between stages so as to maintainY the overallconcentration of water in the reaction system as low as desired,particularly when employing the process for the production ofhydrocarbons. The number of stages employed may range from two to aboutseven.

' In my co-pending application Serial No. 626,425, led November 2, 1945,now U. S. Patent 2,486,894, issued November l, 1949, I have disclosedeffecting hydrogenati'on of lcarbon monoxide in the presence of addedcarbon dioxide and under specified conditions of temperature such as tosuppress methane formation and also such 'as to materially reduce thenet production of carbon dioxide from the process. As there 1'; ofreactants passing to the 'reaction zone substantially greater than, forexample, approximately twice as great as the numerical value of theequilibrium constant for the Water gas shift reaction (CO-l-H2O=CO2{H2)at the'temperature prevailing in the reaction zone or stage,

Where 1c is the fraction of the carbon monoxide which will be convertedin that stage. This fraction converted may range from 0.95 to 0.995.

The equilibrium constant K can be expressed as K=0.0202e with theexponent Synthesis vfeed gas, containing v 2.7183, and T is the reactiontemperature in degrees Fahrenheit.

AThe value of K ranges fromV 70 for a reaction temperature of about 5004F. to a value of 16 for a reaction temperature of about. 700 F., and VisWhen the reactants are subjected to contact with a catalyst comprisingiron powderin a state of dense phase fluidization at a temperatureofabout 600 F., this second ratio should be maintained at least in therange of 60 and above, and advantageously in the range of about 100 to160.

By operating under the aforesaid conditions, the present inventionprovides a means for realizing a much greater conversion of theavailable carbon in the synthesis feed gas into desirable compounds, forexample C2 and higher molecular weight hydrocarbons, than has beenachieved in the conventional manner. Thus, it is contemplated eiectingsubstantially complete 2 mols of hydrogen per mol of carbon monoxide,

disclosed, it is advantageous to maintain the ratio but alsocontemplates maintaining conditions such that carbon dioxide is actuallyconsumed in the reaction.

The amount of carbon dioxide added or recycled'to a reaction stagedepends upon the composition of the synthesis feed gas passing thereto.Thus, Vif the hydrogen present is less than that theoretically requiredto react with the carbon Vmonoxide present to produce olens and water,then the amount of carbon dioxide added or recycled is less since carbondioxide is of necessity produced in the reaction under such conditions.

c In-conventional practice, the synthesis "of hy- :drocarbons fromcarbon monoxide and hydrogen is accompanied by the formation of largeamounts of carbon dioxide and methane as well as water. Carbon dioxideso produced apparently results in some measure from the carbidingreaction between the catalyst metal and carbon monoxide, which reactionis regarded as an essential one in the synthesis from the stand-point ofmaintaining an excess of the carbide in the reaction.

A feature of my invention involves effecting consumption of the carbondioxide so produced in this carbiding reaction by reacting it withavailable hydrogen to form additional carbon monoxide for use in thesynthesis and thus maintain a high concentration of carbon monoxide inthe synthesis reaction zone. Hydrogen may be added so as to assure thepresence of desired hydrogen in the reaction.

However, water is also a product of the reaction between carbon dioxideand hydrogen, and water is also formed to a large extent by otherreactions taking place during the course of the synthesis. Therefore, Icontemplate removing water from the. system substantially as rapidlyasformed. By thus decreasing the concentration of water in the reactionsystem, the reaction between carbon dioxide and hydrogen is enhancedwith consequent increase in the formation of carbon monoxide, which thusoperates to maintain the desired high concentration of carbon monoxidein the reaction. f-

My invention has particular application to the synthesis of valuablehydrocarbons from carbon monoxide and hydrogen by contact with afluidized powdered catalyst at temperatures in the range about 375 to'700 F. and under pressures which may range from atmospheric to severalhundred atmospheres. With an iron catalyst it is advantageous to employtemperatures of about 550 to 600 F.

In carrying out the conversion with a fluidized catalyst for theproduction of hydrocarbons, a synthesis gas stream, advantageouslycontaining at least 2 mols of hydrogen per mol of carbon monoxide, iscontinuously introduced to the lower portion of a vertical reactionvessel containing a mass of catalyst comprising. for example, ironpowder of about 100 to 400 mesh, and having such particle sizedistribution as to assure maintaining uniform uidization of the powderalong the vertical dimension of the reactor. The reactant gas is causedto rise through the catalyst mass under conditions of flow sufiicient tomaintain uidization of the catalyst. The catalyst is maintained undertemperature and pressure such that conversion of carbon monoxide intohvdrocarbons of higher molecular weight than methane occurs. 'Iheresulting products of reaction containing unreacted gas, carbon dioxide,water. and the desired molecular weight hydrocarbons are removed as aneffluent stream from the upper portion of the reaction vessel.

Water is removed from the effluent stream and a gaseous or vaporfraction separated therefrom which contains carbon dioxide, unreactedcarbon monoxide and hydrogen, and which may. if desired, contain atleast some of the lower-boiling hydrocarbons. The resulting residualgaseous or vapor fraction. substantially free from water and containingcarbon dioxide, is passed to the lower portion of a succeeding reactionvessel to which is also passed a stream of fresh synthesis feed gas, aswill be described later with reference to the accompanying drawing.

Carbon dioxide is separated from the effluent stream leaving the finalreactor in the series, and recycled to the initial reactor. Ii desired,por-l tions thereof may be recycled to any one or all of the succeedingreactors. Additional hydrogen may be added to any one or more of thereactors.

The amount of carbon dioxide and hydrogen introduced to each reactor isregulated so as to maintain the previously mentioned molar ratios withrespect to the components of the reactant mixture passing to eachreactor.

By Way of illustration, carbon monoxide and hydrogen are subjected tocontact with a fluidized iron catalyst at al temperature ofapproximately 600 F. and under a pressure of approximately 200 poundsper square inch gauge. In Case I, the feed to the reactor contains about5.8 mol per cent carbon dioxide, and in Case II, the feed contains about26.6 mol per cent of carbon dioxide. The following tabulation comparesthe molar relationships at the inlet to the reaction stage in each caseand also the yields.

Caso I Case II Mols o! Hr Vafsoiga; "'63 ooxruo 1G 164 Yticlrlls incubic centimeter per cubic meter of fresh Ca and heavier hydrocarbons170 222 Water 167 258 Water soluble oxygenated compounds 9 29 Yields asmol peorlzrietrgdcarbon monoxide Case I Case n CO2 20. 9 13. 9 Cri-C1hydrocarbons 16. 6 3.6 C: and heavier hydrocarbons 60. 2 100. 7 Watersoluble oxygenated compounds 2. 3 5. 5

From the foregoing tabulation, it is apparent that the addition of asubstantial quantity of carbon dioxide to the reactor feed eliminatesthe net production of carbon dioxide, and materially reduces theformation of methane. Actually in 1 Case II, carbon dioxide is consumedas indicated by a net disappearance of carbon dioxide to the extent of13.9 mol per cent. 'I'he yield of C3 and heavier hydrocarbons is verymuch larger than in Case I where the feed contained a relatively smallconcentration of carbon dioxide, namely about 5.8 mol per cent.

Reference will now be made to the accompanying drawing which comprises adiagram of flow illustrating one mode of practicing the process of myinvention.

Oxygen or a gas containing a high percentage of molecular oxygen isobtained from a source not shown through a pipe I and is introduced intoa synthesis gas generator 4. Under certain operating conditions in thesynthesis reactors, it is possible to use air for the oxidativecombustion. Therefore, the possibility of using air for the combustionin the synthesis gas generator is included within the scope of theinvention. In most operations, however, the oxidizing gas introducedinto the generator contains over '75% molecular oxygen.

A hydrocarbon gas, which is ordinarily mainly methane, is obtained froma source not shown through a pipe 2 and introduced into the generator 4.

In theigenerator 4, the hydrocarbon gas, which will henceforth .bereferredv to as methane for the sake of simplicity, undergoes controlledoxidative combustion to form synthesis gas containing carbon monoxideand hydrogen in the approximate. mol .ratio of 11:2. Various types ofsynthesis vgas generators may be employed to effeet `fthis Y controlledYoxidative combustion.

Other means vof preparingsynthesis gas may be used such as the reactionbetween coke and steam.

The synthesis gas usually containsa smallpercentagefof carbon dioxideand may also` contain steam vas itissues from the generator 4; Thesynthesis gas, which is at a high temperature after thev oxidativecombustion, is introduced through a pipe 5 into a heat exchanger 6wherein the steam present in the'synthesis gas is condensed.Thecondensed steam is separated from the gases in a gas-liquid separator8 into which it is introduced through 4a pipe l. The Wateris drawn offthrough an exitpipe 9. The synthesis gas, together with the smallpercentage of carbon dioxide present therein, leaves the gas-liquidseparator 8 through'a pipe I0 and passes through the heat exchanger I I1wherein it isreheated to the desired temperature. which thesynthesi'sgas is'preheated may be reduced after the unit is on stream fora time.

The Water content of the synthesis gas is at aminimum so that thedesired ratio ofl reactants may be more readily attained. If thesynthesis gas is saturated With water vapor at 100 F. and 250 pounds-persquare inch gauge, the watercoucentration is only about 0.4% by volume.

The synthesis gas at the desired reaction temperature leaves the heatexchanger 6 through a pipe I2. It is introduced into a plurality ofreactors through this pipe I2 communicating with branch pipes I5, 35and50. The pipe I2 acts as a manifold dividing the Ytotal synthesis feedbetween the diierent reactors. The portion of feed introducedk into eachreactor is proportional to the `number of stages; for example, ina-system utilizing three stages, about 33% ofthe feed is introduced intoeach stage.

During the initiation or starting up of the reaction process, it isnecessary to supply carbon dioxide from an extraneous source in order tomaintain lthe mol per cent of carbor dioxide in the reactor feed to theprimary stage which will satisfy the equations which have been'speciedpreviously, since recycle carbon dioxide may not be availableduring the starting-up period. A convenient source of carbon dioxideisprovided if the hydrogen for the reduction of the catalyst is preparedby subjecting a portionof synthesis gas obtained vfrom the generator 4to reaction with steam at an elevated temperature and pressure so thatthe water gas-shift reaction occurs. Carbon dioxide formed in thisreaction may be separated from the hydrogen through aconventionalabsorp'tion system and after being stripped from theabsorbent may be used to supply the necessary Aconcentration of carbondioxide needed during the initiation of the reaction.

Carbon dioxide so obtained passes along a pipe I6 which serves as aCO2-manifold for lall of the reactors. Usually the carbon dioxide isintroduced in its entirety into the primary reactor 20 through a pipeII, which branches off from pipe theCOz-manifold pipe I6.

' The concentration lof hydrogen is'maintained atthe' concentrationlevel prescribed by the `previously established ratios by introducinghydro- The temperature to 6. gen through a `Hz-manifoldi pipe I4lthrough which the H2 maybe introduced into each'of the reactors.introduced into 'the primary reactor'feed line I5 from the Hz-manifoldpipe I4.

concentration in the, reactor feed is maintained through a recyclestream which is returnedto .ing normally gaseous hydrocarbons andnormally liquid hydrocarbons and also water, together with the excesshydrogen and carbon dioxide,z leaveY the reactor 20 throughfa' pipe 23.'The effluent passes along the pipe 23 to a heat ex'- changer 24 inwhich steam and the normally liquid products of the reactionarecondensed. rIhe total eilluent leaves the heat exchanger 24 through apipe 25 and is introduced into a gas-` liquid separator 26.

In the gas-liquid separator `2li, the gaseous constituents of theeffluent, such as carbon dioxide, hydrogen and the normally gaseoushydrocarbon products of the reaction, which are mainly normally gaseousoleiins, since the formation of methane has been substantially reducedby the conditions of operation of this invention,

are separated from the condensed steam and normally liquid hydrocarbonproducts. The gaseous components leave the gas-liquid separator througha pipe 21.

The liquid components ypass out'of the bottom portion of the separator26 through a pipe 28 and iiow into a decanter'ZS. In the decanter 29,the Water is separated from the normally liquid hydrocarbons and isdischarged through a pipe 30.

TheA normally liquid hydrocarbons leave the decanter 29 through a pipe3l and thereafter join with the liquid hydrocarbons produced in theYother reactors. It is possible, if desired, to introduce a portion ofthe normally liquid hydrocarbons formed in the conversion in the primarystage to a succeeding stage to aid in effecting temperature control by aprocess of evaporative cooling. This may be accomplished by passing aportion of the normally liquid hydrocarbons from the pipe It! into apipe 32 which connects with a pipe 35 which is the feed line to thesecondary reactor. Other means of removing the heat of reaction areusually preferred when employing a fluidized catalystsuch as internalcooling element, for example, through which a fluid heat carrier flowsin indirect heat exchange relationship with the catalyst;

The gaseous components of the eiiiuent, comprising normally gaseoushydrocarbons and the excess-quantities of carbon dioxide and hydrogenWhich'havedirected the reaction in the primary reactor 20 towards theformation of desired compounds, pass along the pipe 2l luntil they reachthe pipe 35 which serves as the fed pipeffor a secondary reactor 35. Thepipe 35 connects'with the manifold pipe l2 through which the totalsynthesisgas is distributed to the Various v*stages of the reaction. l Y

The addition ofthe-gaseous stream to the-'syn- Usually a major portionof the H2 is.

After the unit; has been in operation for a time, the hydrogen thesislgas maintains the concentrations of hydrogen, carbon monoxide andcarbon dioxide in the specied ratios. Since the water formed in theprimary stage has been condensed and removed, the water content of thereactor feed is still negligible, being merely the vapor pressure ofWater remaining after the condensation in the heat exchanger 24.Additionalcarbon dioxide, if needed, may be obtained through a branchpipe 2| which connects with CO2-manifold pipe |6. Additional hydrogen,if needed, may be obtained through a branch pipe 22 which connects withH'z-manifold pipe |4.

At least the major portion of the carbon dioxide and hydrogen which mustbe added to the synthesis gas in order to maintain the prescribed ratiosof concentrations is supplied to the secondary reactor from the gaseouscomponents of the eluent from the first. Thereby, the total quantitiesof carbon dioxide and hydrogen necessary to preserve the concentrationsof components in the prescribed ratios are reduced for the overallconversion of synthesis gas.

e The reactor feed containing the constituents in the prescribedconcentration ratio enters the secondary reactor 36 through the pipe 35.The reactants undergo conversion therein which is directed towards theformation of desired products by the elimination of the net productionof carbon dioxide and the material reduction of the formation ofmethane.

The eiiluent containing the products of reaction, excess carbon dioxideand excess hydrogen leaves the reactor 36 through a pipe 3B. The eiuentthen undergoes treatment which is analogous to that which the eiiiuentfrom the primary reactor 20 undergoes. The effluent passes into a lheatexchanger 39 wherein the steam and normally liquid constituents arecondensed. The eluent then passes to a gas-liquid separator 4| through apipe 40. In the gas-liquid separator 4|, the gaseous components of theeifluent are separated from the condensed hydrocarbons and water. Thesegaseous components leave the separator 4| through a pipe 42.

The condensed portion of efiluent passes into a decanter 44 through apipe 43. 44, the water is separated from the liquid hydrocarbons and isdischarged through a pipe 45.

The liquid hydrocarbons leave the decanter 44 through a pipe 46 andthereafter join with the liquid hydrocarbons which are separated fromthe primary reactor eiiuent. Provision may also be made for introducinga portion of the liquid hydrocarbons into the third reactor to serve asan evaporative coolant by passing a portion of the liquid hydrocarbonsfrom the pipe 46 along a pipe 41 which leads into a pipe 50 which is thefeed line to the tertiary reactor.

The gaseous components of the eiiiuent pass along the pipe 42 whichleads into a pipe 50 which serves as the feed line for the tertiaryreactor 52. The gaseous constituents comprise excess carbon dioxide andhydrogen which latter two have directed the course of the conversiontowards the desired products in both of the previous stages. The carbondioxide and hydrogen in this gaseous stream serve to maintain thedesired ratio of reactant concentrations for the third stage ofconversion.

. The synthesis gas from the generator 4 enters the feed pipe 50 fromthe manifold pipe l2. :Therein it is joined by the gaseous portion ofthe effluent from the secondary reactor 36. Additional carbon dioxide,if needed, may be added In the decanter` to the reactor feed from theCO2-manifold pipe I6. Additional hydrogen, if needed, may be added tothe reactor feed from the Hz-manifold pipe i4. In the reactor 52, thereactants are converted into desired valuable products withsubstantially no net production of carbon dioxide and only limitedformation of methane.

The reactor feed in each succeeding stage is increased by the quantityof gaseoushydrocarbons formed in the preceding stage. Since it isdesirable to conduct the conversion at equivalent velocities in all thestages, it is advantageous to slightly enlarge the reactor in eachsucceeding stage. The extent of this enlargement may be calculated fromthe desired linear velocity and the increment in the reactor feed whichis effected bythe addition of gaseous hydrocarbons to each stage.

The effluent leaves the reactor 52 through a pipe 53. The efiiuentproceeds therealong to a condenser 54 in which liquid hydrocarbons andsteam are condensed. The efliuent then passes into a gas-liquidseparator 56 through a pipe 55. The gaseous components are separatedfrom the condensed portion of the eluent therein. The gaseous componentsleave the separator 56 through a pipe 62. Further treatment of thisgaseous fraction will be described in detail later.

The condensed portion of the eiiluent passes into a decanter 58 througha pipe 51. In the decanter 58, Water is separated from the liquidhydrocarbons and is discharged through a pipe 59.

The liquid hydrocarbons leave the decanter 58 through a pipe 60 and passtherealong until they pass into a manifold pipe 6| into which the liquidhydrocarbons from primary and secondary reactors also flow. 'I'hecombined liquid hydrocarbons may be subjected to conventionalstabilization and fractionation, not shown, or to such other treatmentas may be desired. 'Ihe gases separated from the liquid hydrocarbons inthe stabilization can be introduced into the polymerization unit whichwill be described later.

Returning to the gaseous components of the effluent from the tertiaryreactor 52 which have left the separator 56 through a pipe 62, theycomprise excess carbon dioxide, excess hydrogen and all of the normallygaseous hydrocarbons which have been formed in all three stages of thecatalytic conversion. The gaseous stream is separated into two streams.

One portion, known as Wet gas, passes along a pipe 'I9 which branchesoff from the pipe 62. This Wet gas, comprising carbon dioxide, hydrogenand normally gaseous hydrocarbons, such as propane, butane and pentane,with minor quantities of C1 to C2 hydrocarbons, is recycled to theprimary reactor 20. By returning this Wet gas, a portion of the carbondioxide and hydrogen required to supply the necessary concentrations areprovided.

A portion of the gas stream fiowing through the pipe 62 may be vented orpiped to storage through draw-off pipe 63.

The major portion of the gaseous fraction of the effluent passes alongthe pipe 62 into a, carbon dioxide absorbing unit 15. Therein the carbondioxide contained in the gaseous stream is absorbed in a suitablesolvent such as a monoethanolamine solution. The gaseous hydrocarbonsand hydrogen from which the carbon dioxide has been stripped leave theabsorber 15 through a pipe 16. The further treatment of this materialwill be described in detail later.

Upon regeneration of the absorbent in a regenerator section of theabsorbing unit 15, carbon dioxide is liberated and leaves the absorbingunit 'i5 through a pipe 80.

The carbon dioxide so liberated passes along the pipe 38 through whichit is returned to the CO2-manifold pipe I6. The carbon dioxide is raisedto a required pressure prior to its return to the manifold pipe I6. Amajor portion of recycle carbon dioxide is returned to the primaryreactor 25 through the branch pipe I1 which connects the manifold pipeI6 With the primary reactor feed line I5. By this method, a concentratedsource of carbon dioxide is provided by which the concentration ofcarbon dioxide in the feed to the primary reactor may be maintained atthe necessary level. Provision is made for introducing portions of thiscarbon dioxide as needed into the secondary and tertiary reactors as hasbeen previously described. Excess carbon dioxide may be vented through avent 8|.

The gaseous hydrocarbons and excess hydrogen which have left theCO2-absorber 'I5 through the pipe 16 pass therealong to a polymerizationunit 85. The gaseous hydrocarbons which have been separated from theliquid hydrocarbons by stabilization may also be introduced into thepolymerization unit 85. In the polymerization unit 85, the olens presentin the gaseous hydrocarbons are polymerized by contact with a suitablecatalyst such as phosphoric acid on silica. As a result of thispolymerization pro-cess, the gaseous olefin hydrocarbons form liquidhydrocarbons. f

A gaseous stream, comprising hydrogen, nitrogen, gaseous paraffins andunpolymerized olens, leaves the polymerization unit '85 through a pipe86. A portion of this gas stream is vented to fuel through a vent 81 inorder to prevent the accumulation of nitrogen in the system. The desiredportion of this Hz-rich gas stream passes along the pipe 86 until itreaches the pipe I4 which serves as the E12-manifold for the threereactors. This I-Iz-rich gas stream is mostly diverted to the primaryreactor 20 through the pipe I4 which leads into the primary reactor feedline I5 in order to maintain necessary Hz concentration. Provision ismade for introducing portions of the Hz-rich stream as needed into thesecondary and tertiary reactors as has been previously described.

The liquid hydrocarbons which have been formed by the polymerization ofthe gaseous olens leave the polymerization unit 85 through a pipe 98.Thereafter they are subjected to stabilization and fractionation so asto obtain component fractions such as gasoline, diesel oil, etc.

While specic reference has been made to employing a catalyst comprisingiron, it is contemplated that other synthesis catalysts comprising ametal or metals from the iron group of the periodic system, i. e.,cobalt, nickel, ruthenium etc. may be employed. The metal may beemployed in association with a supporting or carrier material and alsowith suitable promoting agents, if desired.

An effective iron catalyst comprises iron powder of about 100 to 400mesh containing about 1 to 2% of potassium oxide (KzO) and about 2 to 3%alumina (AlzQz). Preferably all Vof the powder should pass through a 100mesh screen and about should pass through a 325 mesh Y' l0 oxides ofthorium, magnesium, uranium and vanadium, while examples of supportingmaterials are diatomaceous earth, silica gel, Filtrols etc.

Thus an example of a supported catalyst would be one comprising about32% cobalt, 64% Filter Cel and about 4% thorium and magnesium oxides.

It is also contemplated that other than nuidized catalyst systems may beused. The catalyst may be employed in either stationary or moving bedform.

Obviously many modifications and variations of the invention, ashereinbefore set forth, may be made without departing from the spiritand scope thereof and, therefore, only such limitations should beimposed as are indicated in the appended claim.

I claim:

The process for the production of desired hydrocarbons, oxygenatedhydrocarbons and mixtures thereof by the catalytic hydrogenation ofcarbon monoxide with the conversion of substantially all of the feedcarbon monoxide into said desired products and with repressed formationof carbon dioxide, which comprises feeding a gaseous mixture of carbonmonoxide, hydrogen, water vapor and carbon dioxide through a reactionzone containing a fluidized solid particle, iron, hydrocarbon synthesiscatalyst, contacting said gaseous mixture with said fiuidized catalystat a reaction temperature in the range about 550- 700 F., until about0.95 to about 0.995 of said feed carbon monoxide has been converted intodesired products of reaction, maintaining the composition of saidgaseous feed mixture such that the molar ratio of hydrogen to carbonmonoxide is at least 2:1, the amount of water vapor is not more thanthat corresponding to saturation at F., and the proportion of carbondioxide is sufficient to repress action of the water gas shift reactionin that direction which consumes carbon monoxide and Water vapor withthe formation of carbon dioxide such that the conversion of the feedcarbon monoxide into undesired carbon dioxide bythe water-gas shiftreaction is substantially inhibited, withdrawing effluent products ofreaction from the reaction zone and recovering the desired products ofreaction therefrom.

CLAUDE W. WATSON.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,213,415 Slatineanu Sept. 3,1940 2,243,869 Keith June 3, 1941 2,244,196 Herbert June 3, 19412,248,099 Linchk July 8, 1941 2,257,293 Dreyfus Sept. 30, 1941 2,318,602Duftschmid et al. May 11, 1943 2,347,682 Gunness May 2, 1944 2,351,248Wirth et a1 June 13, 1944 2,417,164 Huber, Jr. Mar. 11, 1947 OTHERREFERENCES Haslam, R. T., and Russel, R. P., "Fuels and TheirCombustion, First Edition (1926), published by McGraW-Hill, New York,pages -6 (2 pages).

